Manufacture of new dyestuffs and the application thereof



Patented Aug. 14,1934

PATENT. OFFICE.

MANUFACTURE\OF NEW DYES'IUFFS ,TIIE APPLICATION THEREOF Henry Charles Olpin, land, assignor to Spondon, near Derby, Eng- Celanese Corporation oi America, a corporation of Delaware No Drawing. Application January 25, 1930, 'Serial No. 423,547. In Great Britain March 8 Claims.

This invention relates to the manufacture of new azo dyestuffs and the application thereof and more particularly their application to materials made of or containing cellulose acetate or other cellulose esters or ethers.

The new azo dyestuffs of the present invention are characterized in that they contain the tetrahydronaphthalene nucleus and are derived from ar-tetra-hydro-aor p-naphthylamine or derivatives thereof. They may be prepared either by diazotizing an ar-tetra-hydro-aor p-naphthylamine and coupling with a suitable component or by coupling any suitable diazo compound with ar-tetra-hydro-aor p-naphthylamine or a derivative thereof. u

Dyestuffs preparedby using an ar-tetra-hydl'O-czor fi-naphthylamine or other amino compound as coupling component may bev diazotized and coupled either in substance or on the fibre,

0 while those containing groups capable of effecting a coupling may be coupled either in substance or on the fibre with diazo bodies. a The new dyestuffs of the present invention and more particularly the unsulphonated dyestuffs (or. 8-5) a as immunized cotton obtained with p-toluene sulpho-chloride, or methyl, ethyl or benzyl. cellulose or the like, or materials containing cellulose esters or ethers mixed with other fibers. In certain cases mono sulphonated dyestuffs may also be employed.

Dyestuffs prepared by using ar-tetra-hydro-anaphthylamine or a derivative thereof as end component give fuller shades than those obtained by using'the fi-compound or a derivative thereof as end component.

Though the parent amines or amino deriva tives are more closely allied to the corresponding 4 compounds of the benzene series than to'those' of thdnaphthalene series, the new dyestuffs are found to be much superior to the corresponding benzenoid dyestuffs which are in general proncuncedly phototropic. 4

In addition to being applicable in substance, the new dyestuffs may be formed on thematerials themselves, for example by applying both base and developer together and subsequently diazotizin' g, by applyingthe base, diazotizing on g are especially of value for dyeing or otherwise colthe fibre l ng'. Or by applying the coupler so curing materials, made of cellulose acetate or other and devfilopmg h a (ham 3911mm!!- cellulose esters or ethers, for example cellulose The w a e s m amp s f dyes u formate, propionate or butyrate or the products which may be prepared and applied according obtained by the treatment of alkalized cellulose to the present invention, which is however not 0 withesterifying agents, e. g. the product known to be considered as limited thereto. I v 35 Component gggj l robabie structural formula. Shade L i Ar-totrahydro-B-naphtbyl- Phenol Yellow. amine. 4o V n n H AgggghVdro-fl-naphthyl Napht 0] A8 B8 I \(O orange. 50 H on. do i 55 xi-l0 component tifi Probable structural formula Shade NH! P-nitraniline Ar-tegabydro-fi-naphthyl- NOON=N Golden orange.

. I Q 85. N0: m-nitraniline Ar-tetnhydro-a-naphthyl- ON=N NH, Marigold.

\ mine.

p-nitraniline..- Ar-tctrabydroi-mphtbyl- N0 N=N NH: Oran 0.

amino. a

n 11 i g 1 0 nitrlniline-o-sulphonic Ar-ietrah dro-a-na lath 1- NO N= NH O ed.- PM. v p r ne" s in a n n d a i In the case of the last four dyestuifs, similar shades may be obtained by using alkyl derivatives of the ar-tetrahydro-naphthylamines.

The dyestuffs or components may be applied to the materials in the form of aqueous solutions or aqueous solutions oftheir salts, if sufilciently soluble, and in so applying-them any of the usual assistants may be employed. If insufilciently soluble the dvestufis or components may be applied in the form of aqueous suspensions or dispersions produced by any suitable methods. Dispersions of the dyestuffs or components may, for

9 example, be obtained by grinding in the so-called colloid mills, by dissolving in a solvent and mixing with water containing or notcontaining dispersators or protective colloids or by treatment -wi-th dispersators, for example in the manner described in U. S. Patents Nos. 1,618,413, 1,614,414, 1,694,413, 1,690,481 and 1,716,721, and U. 5. Patent applications S. Nos. 152,517 dated 3rd December 1926, 134,138 dated 7th September 1928, 390,423

dated 4th September 1929 and 390,424 dated 4th September, 1929. The compositions of matter containing the relatively insoluble dyestufi's .or an the tetrahydro-naphthylamines or relatively water insoluble derivatives thereof and .containing dispersators and/or protective colloids areincluded in the present invention.

As indicated above dvestufi's containing diazotizable amino groups maybe diazotized on the fibre and developed. Alternatively dyestufis con-- taming-groups capable of eifecting a coupling may be developed on the fibre with the aid of solutions of diazo bodies.

The following examples show the best methods known to me for carrying the invention into effect; but of course they are not be considered as limiting the invention in any way:

. Example 1 v 210 trains of p-nitraniline are dissolved i water with addition of 420 cos. of hydrochloric acid of 22 B., and the solution cooled with ice to 5-10 O. 'I'hevolume is now approximately 3. litres. A solution of grams of technical so- Qdium nitrite (95%) in 1 litre of water is now added 10,

in one lot and the mixture well stirred till a clear solution is obtained. 224 grams of ar-tetrahydro-a-naphthylamine are dissolved in water with theaddition of sufilcient hydrochloric acid to eiIect solution and cooled to 5-10 C. by adding 5 chopped ice. The diazo solution is now run in slowly, mineral acidity being neutralized by addition of sodium acetate solution (test with Congo red paper). When coupling is complete the insoluble dyestufl' is filtered oil, and washed well with water. It is preferably retained as an aqueous paste. Example 2 147 grams ar-tetrahydro p-naphtnvlamine are135 dissolved by warming with 500 ccs. hot water and 300 cos. of concentrated hydrochloric acid, and ice added to bring the temperature to 0 C. '70 grams of sodium nitrite (100%) dissolved in 500 ccs. oi water are now added quickly with stirring, dstirred for a few minutes, when the solution should show a very slight excess of nitrous acid (starch iodide paper) It is now added slowly to a cooled aqueous solution of 116 grams sodium phenate, dilute sodium carbonate solution being 1 T run in at the same time atsuch a rate that slight alkalinity is maintainedthroughout the coupling operation. The precipitated dyestufi is filtered OE, and washed well with cold water. It is preferably retained as an aqueous paste. 1

. Ezcmple3 tions are mixed, diluted to 300 litres with soft water, and sufficient of a 10% solution of acetic acid added to neutralize most of the alkali, but still maintain a slight alkaline reaction. The bath is heated to 7580 C. and 10 kilograms of cellulose acetate knit fabric entered, and treated for 2 hours at -85 C. The goods are 'now rinsed well and immersed in a cold bath containing 4 grams per litre of sodium nitrite and 8 cos. per litre of glacial acetic acid. They are worked for hour in this bath, during which time the colour develops slowly. Coupling may be completed advantageously by transferring to a cold bath containing 1 gram per litre of sodium carbonate, and working till the desired shade is obtained. The goods, which are now dyed an orange shade, are rinsed, soaped lightly, and dried or otherwise treated as requisite.

Example 4 I To dye an orange shade on 10 kilos of cellulose acetate yarn in hank form:-

200 grams of the dyestuff obtained by coupling diazotized p-nitraniline-o-sulphonic acid with ar-tetrahydro-a-naphthylamine are dissolved as the sodiumsalt in 300 litres of water at 50-60 C. the goods entered and the temperature raised slowly to 80 C. Glaubers salt up to 40% and acetic acid up to 2-3%, both on the weight of goods, may be added as necessary to exhaust. When the desired shade is achieved the goods are lifted, rinsed and dried or otherwise treated as requisite.

Example 5 To dye a marigold shade on 10 kilos of cellulose acetate knit fabric.

grams of finely ground dyestuff obtained by coupling diazotized m-nitraniline with ar-tetrahydro-a-naphthylamine are well stirred with 1 kilo of Turkey red oil (50%) the mixture is heated, with stirring until a good dispersion is obtained, then diluted with boiling soft water and passed through a filter cloth into a dyebath containing 300 litres of soft water. The material is entered, and dyeing carried out as usual, the temperature being raised slowly to 80 C., and the fabric processed at this temperature till the de sired shade is achieved. The goods are now lifted, rinsed and dried or otherwise treated as requisite.

, What I claim and desire to secure by Letters Patent is:--

1. Process for coloring materials containing an organic derivative of cellulose which comprises applying thereto unsulphonated azo dyestuffs containing the tetrahydronaphthalene nucelus.

2. Process for coloring materials containing an organic derivative of cellulose which comprises forming unsulphonated azo dyes thereon by coupling on the materials a compound of the artetrahydro-naphthylamine series with a further component.

3. Process for coloring materials containing an organic derivative of cellulose which comprises applying thereto unsulphonated azo dyestuffs obtainable by coupling a compound of the ar-tetrahydro-a-naphthylamine series with a further component.

4. Process for coloring materials containing cellulose acetate which comprises applying thereto unsulphonated azo dyestuffs containing the tetrahydronaphthalene nucleus.

5. Process for coloring materials containing cellulose acetate which comprises formingon the materials unsulphonated azo dyestuffs containing 

